CN101716528A - Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof - Google Patents
Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof Download PDFInfo
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- CN101716528A CN101716528A CN200910236255A CN200910236255A CN101716528A CN 101716528 A CN101716528 A CN 101716528A CN 200910236255 A CN200910236255 A CN 200910236255A CN 200910236255 A CN200910236255 A CN 200910236255A CN 101716528 A CN101716528 A CN 101716528A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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Abstract
The invention discloses a catalyst system of chloroethylene prepared by hydrochlorinating acetylene and a preparation method and application thereof. The catalyst system comprises a catalyst carrier and a catalyst, wherein the catalyst carrier is imidazole ion liquid and the catalyst is any combination of one or more of gold, platinum, palladium, tin, mercury, copper or rhodium chlorides. The preparation method of the catalyst system is to dissolve the catalyst into the catalyst carrier. Acetylene and chlorine hydride are mixed and react in the presence of the catalyst system. The preparation process realizes a liquid phase reaction for preparing chloroethylene by hydrochlorinating acetylene, avoids the loss of the catalyst system, is more environment-friendly and safer, and improves the conversion rate of the acetylene and the selectivity of the chloroethylene.
Description
Technical field
The present invention relates to a kind of catalyst system and preparation and application of preparing chloroethylene by acetylene hydrochlorination.
Background technology
VCM is important organic synthesis industrial chemicals, is used to produce polyvinyl chloride, and polyvinyl chloride is the important kind of plastics.The acetylene hydrochlorination reaction is the important chemical process of industrial synthesizing chloroethylene, and the most polyvinyl chloride raw materials of China are produced by this reaction.The catalyst that at present should reaction adopts is the mercuric chleride catalyst that loads on the active carbon, react to be gas-solid reaction, the catalytic reaction of in fixed bed, carrying out have catalytic activity height, reaction speed soon, react violent characteristics.But, reaction zone narrow (be generally that 0.15m～0.7m), reaction heat take away that difficulty, local temperature are difficult to control, the mercury chloride distillation in the catalyst is fast, thereby cause catalyst weak point in service life, consume height, environment is brought significant damage, simultaneously the active carbon mutability.Gas-solid reaction uses active carbon to be carrier, and active carbon is limited to the adsorption capacity of catalyst, and before the use, the mercuric chleride catalyst system that loads on the active carbon needs heat-activated 8-12 hour; In the use, the easy efflorescence of catalyst system, easy surperficial carbon deposit, easily hardening need often be turned over and be smash, and causes catalyst loss; After the use, catalyst be adsorbed on be unfavorable on the active carbon reclaiming (Agnew J.B., et al., Catalyst deactivation inacetylene hydrochlorination, Ind.Eng.Chem.Prod.Res.Dev., 1986,25:19-22.).
Compare with traditional fixed bed reactors, the liquid-phase catalysis reaction system is not used solid carrier, and heat-transfer effect is good, and it is too high to avoid local temperature occurring, reduces the catalyst distillation, thereby prolongs catalyst service life, reduces consuming, and has not only saved cost but also environmental protection; Do not use absorbent charcoal carrier, problem such as avoided its efflorescence that brings, harden, easy and simple to handle; Catalyst after the use can reclaim and regenerate.
The liquid-phase catalyst system of acetylene hydrochlorination reaction also had report in the past.As:
Patent US 1812542, and it is vinyl chloride as catalyst with acetylene conversion that US 1934324 and US 3113158 have introduced the aqueous hydrochloric acid solution that is dissolved with copper chloride, stannous chloride.Patent CN1037501 is dissolved in the N-methyl pyrrolidone as catalyst with palladium bichloride, realizes the liquid phase hydrochlorination.SU 165446 and SU 232956 have reported respectively in the presence of copper chloride, the acetylene hydrochlorination reaction in dimethyl formamide and hydrochloric acid three ethanolic solutions.
The acetylene hydrochlorination reaction temperature is higher, industrially is generally 150～180 ℃, all is that OOS or water are as catalyst dispersion and these patents are used, and the solvent boiling point that has is low, as water, ethanol; The solvent that has volatilizees under reaction temperature seriously, causes the loss of solvent, needs to increase cooling device, increases cost, and has limited the selection of reaction temperature, and cause environmental pollution.In addition, in a single day the leakage accident takes place in organic solvent, seriously polluted, fire hazardous.
Ionic liquid is at room temperature or near be in a liquid state serviceability temperature the material that is made of ion, its character can all can be changed by the structure that changes ion as fusing point, viscosity, density, hydrophobicity by cation modified or change anion are regulated.
Summary of the invention
In order to solve in the prior art existing problem in the preparing chloroethylene by acetylene hydrochlorination reaction, the invention provides a kind of catalyst system and preparation and application of preparing chloroethylene by acetylene hydrochlorination.
The catalyst system of preparing chloroethylene by acetylene hydrochlorination provided by the invention comprises catalyst and catalyst carrier, and wherein, catalyst carrier is a glyoxaline ion liquid.
As preferably, the said catalyst carrier anion is the glyoxaline ion liquid of chlorion, bromide ion, hexafluoro-phosphate radical or tetrafluoroborate.Specifically optional, a kind of or its two or more any combinations in chlorination 1-butyl-3-methylimidazole, bromination 1-butyl-3-methylimidazole, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate or 1-ethyl-3-methylimidazole tetrafluoro phosphate.
Above-mentioned catalyst is a kind of or its two or more any combinations in the chloride of gold, platinum, palladium, tin, mercury, copper or rhodium, and wherein, the concentration of catalyst in described catalyst system is 0.02～1mol/L.
The invention provides a kind of method for preparing above-mentioned catalyst system:, above-mentioned catalyst is dissolved in the said catalyst carrier according to described concentration.
As preferably, above-mentioned catalyst system also comprises a kind of or its two or more any combinations in the chloride of bismuth, potassium or cerium as co-catalyst, and wherein, the concentration of above-mentioned co-catalyst in above-mentioned catalyst system is 0.0045～0.5mol/L.
The method for preparing above-mentioned catalyst system is: according to described concentration, above-mentioned catalyst and co-catalyst are dissolved in the said catalyst carrier.
Adopt the catalyst system of above-mentioned preparing chloroethylene by acetylene hydrochlorination to prepare vinyl chloride, preparation process is: with mol ratio is after 1: 1 to 1: 3 acetylene and hydrogen chloride mix, react in the presence of the catalyst system of above-mentioned preparing chloroethylene by acetylene hydrochlorination, reaction temperature is 100 to 200 ℃.As preferably, the preparation process that the catalyst system of above-mentioned preparing chloroethylene by acetylene hydrochlorination prepares vinyl chloride is: with mol ratio is after 1: 1.2 to 1: 1.5 acetylene and hydrogen chloride mix, react in the presence of the catalyst system of above-mentioned preparing chloroethylene by acetylene hydrochlorination, reaction temperature is 150 to 180 ℃.
The technique effect that the present invention reached:
1, catalyst system preparation method provided by the invention is simple, carries out the reaction of preparing chloroethylene by acetylene hydrochlorination in the presence of above-mentioned catalyst system, has improved the selectivity of the conversion ratio and the vinyl chloride of acetylene;
2, realize liquid phase reactor, avoiding with the active carbon is that the gas-solid reaction of carrier brings heat to concentrate, thereby has suppressed the volatilization of catalyst;
3, catalyst system can be directly used in the acetylene hydrochlorination reaction, has omitted the activation step of catalyst system in the prior art, has simplified the processing step of reaction;
4, catalyst system has bigger equilibrium temperature scope, better chemical stability, in use avoids catalyst system generation sex change and influences reaction result;
5, catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt free of losses in the use, and safety and environmental protection;
6, do not contain organic solvent in the catalyst system, do not have combustibility, no ignition point, safe in utilization, even taking place, leakage accident also avoids causing bigger harm;
7, simplify consersion unit.
The specific embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments, can be implemented so that those skilled in the art can better understand the present invention also, but illustrated embodiment is not as a limitation of the invention.
The present invention is divided into four classes by cationic difference with ionic liquid: [NR
4]+(quaternary ammonium alkyl) class ionic liquid, [PR
4]+(alkyl quaternary phosphine) class ionic liquid, glyoxaline ion liquid and pyridines ionic liquid.
The present invention is further illustrated below by embodiment.
Embodiment 1
(1) preparation of catalyst system:
The copper chloride of 3.1928g is dissolved in chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid of 28.1577g, copper chloride concentration is 0.54mol/L, is to dissolve 1h in 100 ℃ of oil baths in temperature.
(2) acetylene hydrochlorination reaction:
Above-mentioned catalyst system is directly used in the reaction of acetylene hydrochlorination generation vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.7, air speed 14mL/mLh reacts under 150 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 35-40%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 2
(1) preparation of catalyst system:
The stannous chloride of 3.2308g is dissolved in chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid of 22.9236g, stannous chloride concentration is 0.92mol/L.In temperature is to dissolve 2h in 120 ℃ of oil baths.
(2) acetylene hydrochlorination reaction:
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.43, air speed 19mL/mLh reacts under 160 ℃ condition, hydrogen chloride soak time 1.1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 25-35%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 3
(1) preparation of catalyst system:
The 1g platinum tetrachloride is dissolved in 31.3710g chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid, and platinum tetrachloride concentration is 0.039mol/L.In temperature is to dissolve 2h in 120 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.2, air speed 6.8mL/mLh reacts under 170 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 55-60%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 4
(1) preparation of catalyst system:
The gold trichloride of 1g is dissolved in chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid of 28.3492g, gold trichloride concentration is 0.075mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.7, air speed 11mL/mLh reacts under 170 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 55-60%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 5
(1) preparation of catalyst system:
The mercury chloride of 3.7768g is dissolved in chlorination 1-butyl-3-methylimidazole [Bmim] Cl ionic liquid of 25.4221g, mercury chloride concentration is 0.34mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 7.5mL/mLh reacts under 159 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 53-60%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 6
(1) preparation of catalyst system:
The mercury chloride of 1.9112g is dissolved in chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid of 25.4221g, mercury chloride concentration is 0.22mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.33, air speed 35mL/mLh reacts under 158 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 35-40%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 7
(1) preparation of catalyst system:
The 3.4372g palladium bichloride is dissolved in 28.1577g chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid, and palladium bichloride concentration is 0.46mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.2, air speed 20mL/mLh reacts under 150 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 57-60%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 8
(1) preparation of catalyst system:
3.7753g mercury chloride is dissolved in 25.4221g chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid, and mercury chloride concentration is 0.34mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths, adds the potassium chloride of 0.2692g, and potassium chloride concentration is 0.0919mol/L, dissolving 0.5h.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 13mL/mLh reacts under 159 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 57-65%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 9
(1) preparation of catalyst system:
The 1g gold trichloride is dissolved in 29.6394g chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid, and gold trichloride concentration is 0.0719mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.Add the 0.3293g copper chloride again, copper chloride concentration is 0.0532mol/L, dissolving 0.5h.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.7, air speed 11mL/mLh reacts under 170 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 65-70%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 10
(1) preparation of catalyst system:
3.7324g copper chloride, 1.25g potassium chloride, 0.06g cerium chloride are dissolved in 30.1385g chlorination 1-butyl-3-methylimidazole [Bmim] Cl ionic liquid, copper chloride concentration is 0.59mol/L, potassium chloride concentration is 0.36mol/L, and cerium chloride concentration is 0.0045mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1, air speed 15mL/mLh reacts under 100 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 38-44%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 11
(1) preparation of catalyst system:
0.5g platinum tetrachloride, 3.25g mercury chloride are dissolved in 27.8121g chlorination 1-butyl-3-methylimidazole [Bmim] Cl ionic liquid, and platinum tetrachloride concentration is 0.028mol/L, and mercury chloride concentration is 0.28mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/3, air speed 15mL/mLh reacts under 180 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 61-67%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 12
(1) preparation of catalyst system:
The 3.0734g stannous chloride is dissolved in 15.2158g chlorination 1-butyl-3-methylimidazole [Bmim] Cl ionic liquid, is to dissolve 1h in 100 ℃ of oil baths in temperature, adds 16.3952g 1-ethyl-3-methylimidazole tetrafluoro phosphate [Emim] PF again
6Ionic liquid and 0.3026g potassium chloride, dissolving 0.5h, stannous chloride concentration is 0.82mol/L, potassium chloride concentration is 0.118mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.7, air speed 11mL/mLh reacts under 156 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 45-50%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 13
(1) preparation of catalyst system:
The copper chloride of 3.1331g being dissolved in chlorination 1-butyl-3-methylimidazole [Bmim] Cl ionic liquid of 14.0175g, is to dissolve 1h in 100 ℃ of oil baths in temperature, adds 1-ethyl-3-methylimidazole tetrafluoro phosphate ([Emim] PF of 18.0318g again
6) potassium chloride of ionic liquid and 0.3069g, dissolving 0.5h, the concentration of copper chloride is 0.63mol/L, the concentration of potassium chloride is 0.121mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 14mL/mLh reacts under 159 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 44-49%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 14
(1) preparation of catalyst system:
The 3.1928g copper chloride is dissolved in 28.1577g bromination 1-butyl-3-methylimidazole ([Bmim] Br) ionic liquid, and copper chloride concentration is 0.58mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.7, air speed 14mL/mLh reacts under 150 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 35-40%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 15
(1) preparation of catalyst system:
4.0301g radium chloride, 0.13g bismuth chloride are dissolved in 50.22g1-ethyl-3-methylimidazole hexafluorophosphate 33.75 ([Emim] PF
6) in the ionic liquid, radium chloride concentration is 0.57mol/L, bismuth chloride concentration is 0.0122mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.2, air speed 25mL/mLh reacts under 180 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 55-62%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 16
(1) preparation of catalyst system:
The mercury chloride of 1.8501g is dissolved in 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] BF of 42.0789g
4) in the ionic liquid, mercury chloride concentration is 0.21mol/L.In temperature is to dissolve 0.5h in 120 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.33, air speed 35mL/mLh reacts under 158 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 30-45%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 17
(1) preparation of catalyst system:
The mercury chloride of 3.6692g being dissolved in 1-butyl-3-methyl imidazolium tetrafluoroborate [Bmim] Cl ionic liquid of 12.9799g, is to dissolve 1h in 100 ℃ of oil baths in temperature, adds 1-ethyl-3-methylimidazole hexafluorophosphate [Emim] PF of 23.4901g
6Ionic liquid, dissolving 0.5h, mercury chloride concentration is 0.34mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 19mL/mLh reacts under 156 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 42-48%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 18
(1) preparation of catalyst system:
The mercury chloride of 1.8780g is dissolved in 1-ethyl-3-methylimidazole hexafluorophosphate ([Emim] PF of 48.8902g
6) in the ionic liquid, mercury chloride concentration is 0.21mol/L.In temperature is to dissolve 48h in 120 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.33, air speed 35mL/mLh reacts under 170 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 10-20%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 19
(1) preparation of catalyst system:
The 3.1331g stannous chloride is dissolved in 14.0175g chlorination 1-butyl-3-methylimidazole [Bmim] Cl ionic liquid, is to dissolve 1h in 100 ℃ of oil baths in temperature, adds 18.0318g1-ethyl-3-methylimidazole tetrafluoro phosphate ([Emim] PF again
6) ionic liquid and 0.3069g potassium chloride, dissolving 0.5h, the concentration of stannous chloride is 0.49mol/L, the concentration of potassium chloride is 0.122mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 14mL/mLh reacts under 159 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 37-42%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 20
(1) preparation of catalyst system:
The 0.1497g gold trichloride is dissolved in 36.7g1-ethyl-3-methylimidazole tetrafluoro phosphate ([Emim] PF
6) in the ionic liquid, gold trichloride concentration is 0.02mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.7, air speed 11mL/mLh reacts under 170 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 35-40%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 21
(1) preparation of catalyst system:
The mercury chloride of 11.07g is dissolved in chlorination 1-butyl-3-methylimidazole ([Bmim] Cl) ionic liquid of 26.325g, mercury chloride concentration is 1mol/L.In temperature is to dissolve 1h in 100 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.33, air speed 35mL/mLh reacts under 158 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 68-75%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 22
(1) preparation of catalyst system:
The mercury chloride of 1.8501g is dissolved in 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] BF of 42.0789g
4) in the ionic liquid, mercury chloride concentration is 0.21mol/L.In temperature is to dissolve 0.5h in 120 ℃ of oil baths.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.33, air speed 35mL/mLh reacts under 158 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 30-45%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 23
(1) preparation of catalyst system:
The copper chloride of 3.15g is dissolved in chlorination 1-butyl-3-methylimidazole [Bmim] Cl ionic liquid of 25.393g, in temperature is to dissolve 1h in 100 ℃ of oil baths, adds the potassium chloride of 1.462g again, dissolving 0.5h, the concentration of copper chloride is 0.594mol/L, and the concentration of potassium chloride is 0.5mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 14mL/mLh reacts under 159 ℃ condition, hydrogen chloride soak time 1h.Analytical reactions tail gas, the conversion ratio that obtains acetylene are at 44-49%, and the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
Embodiment 24
(1) preparation of catalyst system:
Calcium chloride and copper chloride are dissolved among 27.39g chlorination 1-butyl-3-methylimidazole [Bmim] Cl, are to dissolve 1h in 100 ℃ of oil baths in temperature, and the concentration of calcium chloride is 3.19mol/L, and the concentration of copper chloride is 2.62mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 2.4mL/mLh, 65 ℃ of reaction temperatures.Analytical reactions tail gas, obtaining conversion of alkyne is 47.84%, the vinyl chloride selectivity is greater than 99%.
Weighing to catalyst system in the reaction back, does not have mass loss.Catalyst system does not almost have vapour pressure, and non-volatile, colourless, nothing is smelt, and has bigger equilibrium temperature scope, better chemical stability, in use sex change does not take place and reaction is caused adverse effect in catalyst system, and there is not combustibility, no ignition point, safe in utilization.In the course of reaction, catalyst system is stable, free of losses, uses continuously 720 hours, and the conversion ratio of acetylene and the selectivity of vinyl chloride all do not have reduction.
As follows at the contrast experiment that technical scheme of the present invention is done:
The contrast experiment 1
(1) preparation of catalyst system
Dissolve in hydrochloric acid, calcium chloride, copper chloride in 600g water, concentration of hydrochloric acid is 11.74mol/L, and calcium chloride concentration is 3.19mol/L, and copper chloride concentration is 2.62mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.5, air speed 2.4mL/mLh, 65 ℃ of reaction temperatures.Analytical reactions tail gas, obtaining conversion of alkyne is 34.52%, the vinyl chloride selectivity is 86%.
Catalyst system is weighed mass loss 20% before and after the reaction.Catalyst system used after 120 hours, and conversion of alkyne is 24.3%, and the vinyl chloride selectivity is 77%.
The contrast experiment 2
(1) preparation of catalyst system:
The 3.4372g palladium bichloride is dissolved in the 28.1577g N-methyl pyrrolidone, and palladium bichloride concentration is 0.46mol/L.
(2) acetylene hydrochlorination reaction
The catalyst system that above-mentioned steps prepares is used for the reaction that acetylene hydrochlorination generates vinyl chloride, and the mol ratio of reaction distribution is C
2H
2/ HCl=1/1.2, air speed 20mL/mLh reacts under 120 ℃ condition, hydrogen chloride soak time 1.5h.Analytical reactions tail gas, the conversion ratio that obtains acetylene is 41%, vinyl chloride selectivity 83%.
Catalyst system is weighed mass loss 13% before and after the reaction.Catalyst system used after 240 hours, and conversion of alkyne is 31.2%, and the vinyl chloride selectivity is 78%.
The above embodiment is the preferred embodiment that proves absolutely that the present invention lifts, and protection scope of the present invention is not limited thereto.Being equal to that those skilled in the art are done on basis of the present invention substitutes or conversion, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. the catalyst system of an acetylene hydrochlorination preparing chloroethylene comprises catalyst and catalyst carrier, it is characterized in that, described catalyst carrier is a glyoxaline ion liquid.
2. the catalyst system of preparing chloroethylene by acetylene hydrochlorination according to claim 1 is characterized in that, described catalyst carrier is that anion is the glyoxaline ion liquid of chlorion, bromide ion, hexafluoro-phosphate radical, tetrafluoroborate or tetrafluoro phosphate radical.
3. the catalyst system of preparing chloroethylene by acetylene hydrochlorination according to claim 1, it is characterized in that described catalyst carrier is a kind of or its two or more any combinations in chlorination 1-butyl-3-methylimidazole, bromination 1-butyl-3-methylimidazole, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate or 1-ethyl-3-methylimidazole tetrafluoro phosphate.
4. according to the catalyst system of the described acetylene hydrochlorination preparing chloroethylene of claim 1, it is characterized in that described catalyst is a kind of or its two or more any combinations in the chloride of gold, platinum, palladium, tin, mercury, copper or rhodium.
5. according to the catalyst system of the described acetylene hydrochlorination preparing chloroethylene of claim 4, be characterised in that the concentration of described catalyst in described catalyst system is 0.02～1mol/L.
6. according to the catalyst system of the described acetylene hydrochlorination preparing chloroethylene of claim 1, it is characterized in that described catalyst system comprises that also a kind of or its two or more any combinations in the chloride of bismuth, potassium or cerium are as co-catalyst.
7. according to the catalyst system of the described acetylene hydrochlorination preparing chloroethylene of claim 6, it is characterized in that the concentration of described co-catalyst in described catalyst system is 0.0045～0.5mol/L.
8. the method for the catalyst system of each described acetylene hydrochlorination preparing chloroethylene of preparation claim 1-5 is characterized in that, according to described concentration, with described catalyst dissolution in described catalyst carrier.
9. the method for the catalyst system of preparing chloroethylene by acetylene hydrochlorination described in the preparation claim 7 is characterized in that, according to described concentration, described catalyst and co-catalyst is dissolved in the described catalyst carrier.
10. preparing chloroethylene by acetylene hydrochlorination is characterized in that, adopts the catalyst system of the described preparing chloroethylene by acetylene hydrochlorination of claim 1.
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| PCT/CN2010/073705 WO2011050614A1 (en) | 2009-10-30 | 2010-06-09 | Catalyst system for preparing chloroethylene by acetylene hydrochlorination, preparation method and application thereof |
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| WO2011050614A1 (en) | 2011-05-05 |
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